Photon extraction from ultraviolet light-emitting devices

ABSTRACT

In various embodiments, a layer of organic encapsulant is provided over a surface of an ultraviolet (UV) light-emitting semiconductor die, and at least a portion of the encapsulant is exposed to UV light to convert at least some of said portion of the encapsulant into non-stoichiometric silica material. The non-stoichiometric silica material includes silicon, oxygen, and carbon, and a carbon content of the non-stoichiometric silica material is greater than 1 ppm and less than 40 atomic percent.

RELATED APPLICATION

This application claims the benefit of and priority to U.S. ProvisionalPatent Application No. 62/027,968, filed Jul. 23, 2014, the entiredisclosure of which is hereby incorporated herein by reference.

TECHNICAL FIELD

In various embodiments, the present invention relates to light emittersemitting ultraviolet (UV) radiation.

BACKGROUND

The output powers, efficiencies, and lifetimes of short-wavelengthultraviolet light-emitting diodes (UV LEDs), i.e., LEDs that emit lightat wavelengths less than 350 nm, based on the nitride semiconductorsystem remain limited due to high defect levels in the active region.These limitations are particularly problematic (and notable) in devicesdesigned to emit at wavelengths less than 270 nm. Most developmenteffort has been carried out on devices formed on foreign substrates suchas sapphire where defect densities remain high despite innovative defectreduction strategies. These high defect densities limit both theefficiency and the reliability of devices grown on such substrates.

The recent introduction of low-defect, crystalline aluminum nitride(AlN) substrates has the potential to dramatically improve nitride-basedoptoelectronic semiconductor devices, particularly those having highaluminum concentration, due to the benefits of having lower defects inthe active regions of these devices. For example, UV LEDspseudomorphically grown on AlN substrates have been demonstrated to havehigher efficiencies, higher power and longer lifetimes compared tosimilar devices formed on other substrates. Generally, thesepseudomorphic UV LEDs are mounted for packaging in a “flip-chip”configuration, where the light generated in the active region of thedevice is emitted through the AlN substrate, while the LED dies havetheir front surfaces bonded to a polycrystalline (ceramic) AlN submount.Because of the high crystalline perfection that is achievable in theactive device region of such devices, internal efficiencies greater than60% have been demonstrated. Unfortunately, the photon-extractionefficiency is often still very poor in these devices, ranging from about4% to about 15% achieved using surface-patterning techniques.

For several reasons, the photon extraction efficiency fromshort-wavelength UV LEDs is poor compared to visible LEDs. Thus, thecurrent generation of short-wavelength UV LEDs has low wall-plugefficiencies (WPEs) of, at best, only a few percent, where WPE isdefined as the ratio of usable optical power (in this case, emitted UVlight) achieved from the diode divided by the electrical power into thedevice. The WPE of an LED may be calculated by taking the product of theelectrical efficiency (η_(el)), the photon extraction efficiency(η_(ex)), and the internal efficiency (IE); i.e., WPE=η_(el)×η_(ex)×IE.The IE itself is the product of current injection efficiency η_(inj))and the internal quantum efficiency (IQE); i.e., IE=η_(inj)×IQE. Thus, alow η_(ex) will deleteriously impact the WPE even after the IE has beenimproved via the reduction of internal crystalline defects enabled by,e.g., the use of the AlN substrates referenced above as platforms forthe devices.

Several issues may contribute to low photon-extraction efficiency.First, even the highest-quality AlN substrates available generally havesome absorption in the UV wavelength range, even at wavelengths longerthan the band edge in AlN (which is approximately 210 nm). Thisabsorption tends to result in some of the UV light generated in theactive area of the device being absorbed in the substrate, hencediminishing the amount of light emitted from the substrate surface.Additionally, UV LEDs suffer because approximately half of the generatedphotons are directed toward the p-contact and absorbed by the p-GaN ofthat contact. Even when photons are directed toward the AlN surface,only about 9.4% generally escape from an untreated surface due to thelarge index of refraction of the AlN, which results in a small escapecone. Additional photons are lost on their way to the exit surface dueto absorption in the AlN substrate. These losses are multiplicative andthe average photon extraction efficiency is only about 2.5%.

In typical LED fabrication, the large difference in the index ofrefraction between the LED structure and air (and resulting lack ofphoton extraction) may be greatly ameliorated by using an encapsulantwith an intermediate index of refraction. Specifically, manyconventional designs feature a “dome” of the encapsulant materialdisposed over and at least partially surrounding the LED (andsubsequently cured by a thermal treatment). The encapsulation increasesthe critical angle of total internal reflection through the top surfaceof the semiconductor die, which has led to significant improvements inphoton-extraction efficiency for visible LEDs.

Unfortunately, LED encapsulants and adhesives may be easily damaged byUV radiation, leading to degradation of the encapsulant or adhesive. Thedegradation is particularly severe with exposure to UVC radiation (i.e.,radiation at wavelengths less than 300 nm). Thus, using an encapsulantto improve photon extraction is typically ineffective with UV LEDs.Moreover, although UV-resistant encapsulants have been developed, eventhese compounds exhibit degradation upon exposure to UV light far lessthan the desired service lifetime of UV LEDs. For example, the DeepUV-200 encapsulant available from Schott North America, Inc. ofElmsford, N.Y., exhibits a 15% drop in transmittance for 300 nm lightafter only 1000 hours of exposure.

Thus, there is a need for an easily implementable approach toeffectively increase the photon-extraction efficiency from UV LEDs thatovercomes the lack of stable encapsulants that are transparent to UVradiation, particularly UVC radiation. Such an approach would desirablyenable high transmittance and reliability of UV LEDs without significantdegradation over the intended service lifetime of these devices, e.g.,approximately 10,000 hours or even longer.

SUMMARY

In various embodiments of the present invention, the photon-extractionefficiency of UV light-emitting devices such as UV LEDs is improved viaattachment of an inorganic (and typically rigid) lens directly to theLED die using a thin layer of an encapsulant (e.g., an organiccompound). In some embodiments, the encapsulant is a liquid or gel,e.g., silicone oil and/or silicone resin. The lens typically includes,consists essentially of, or consists of a UV-transparent (at leastUVC-transparent) material such as sapphire, fused silica, or quartz.Other lens materials may be utilized, e.g., materials having an index ofrefraction greater than 1.3 and that are transparent and stable duringexposure to high intensity short-wavelength UV radiation. Utilization ofthe lens results in at least a doubling (and even up to 2.6× or evenlarger increases) in the extracted quasi-continuous-wave output power ofUV LEDs. In addition, the far field pattern (FWHM) of the devices may benarrowed by at least 20%. The lens is preferably shaped to minimize theamount of radiation which will undergo total internal reflection.Typically, this will be a round or hemispherical shape, although othershapes fall within the scope of the present invention. In variousembodiments, the lens shape has a cylindrical component and ahemispherical component in order to, e.g., narrow the far field pattern.In other embodiments, the lens includes, consists essentially of, orconsists of a substantially flat plate or a flat plate that has beenpatterned or textured to enhance light extraction therefrom. Forexample, the flat plate may be patterned to form a Fresnel lens toimprove photon extraction for photons that are approaching the surfaceat a large angle.

Various embodiments of the invention incorporate an organic encapsulantthat degrades upon initial exposure to UV light; in particular, suchorganic encapsulants may experience partial oxidation when exposed to UVlight (e.g., during an initial period of light emission by the device),altering the refractive index of the encapsulant and/or forming smalllocalized areas from which light from the device die scatters,decreasing the amount of UV light reaching the lens and ultimately beingemitted therefrom. In accordance with various embodiments of theinvention, such encapsulants are surprisingly and advantageously atleast partially converted to a non-stoichiometric silica material viaadditional exposure to UV light, improving their output characteristics.Specifically, the carbon content of the encapsulant diminishes to, forexample, approximately 40 atomic % or less, approximately 30 atomic % orless, or even approximately 20 atomic % or less as the encapsulant is atleast partially converted into the non-stoichiometric silica materialduring this initial “burn-in” period of exposure to UV light, andafterward the transmissivity of the encapsulant improves considerablyand is robust for at least thousands of hours of operation of thedevice. In various embodiments, the carbon content of the encapsulantafter conversion into the non-stoichiometric silica material isapproximately 5 atomic % or larger, approximately 10 atomic % or larger,or approximately 15 atomic % or larger. Thus, in accordance with variousembodiments of the present invention, the converted encapsulant issubstantially immune to further UV-induced decreases in transmissivityafter being exposed to UV light for an initial period (e.g., up toapproximately 200 hours, up to approximately 300 hours, or betweenapproximately 100 hours and approximately 200-300 hours). In accordancewith various embodiments of the invention, the non-stoichiometric silicamaterial includes, consists essentially of, or even consists of silicon,oxygen, and carbon, where the carbon content is greater than 1 ppm (andtypically greater than 1 atomic %) and approximately 30 atomic % orless, or even approximately 20 atomic % or less. With long exposures tothe UV light, the composition of the non-stoichiometric silica materialapproaches that of pure silica, but small amounts of carbon may bedetectable via characterization methods such as secondary ion massspectroscopy (SIMS).

Embodiments of the present invention utilize UV light having awavelength selected from the range of approximately 100 nm toapproximately 400 nm. Preferred embodiments utilize UVC light having awavelength selected from the range of approximately 100 nm toapproximately 280 nm, or, even more preferably, approximately 210 nm toapproximately 280 nm. Other embodiments utilize UVA light (i.e., lighthaving a wavelength selected from the range of approximately 315 nm toapproximately 400 nm) or UVB light (i.e., light having a wavelengthselected from the range of approximately 280 nm to approximately 315nm).

In some embodiments, the conversion of the encapsulant embrittles theencapsulant, and thus the lens may be more likely to loosen or becomedetached from the light-emitting die. In such embodiments, an additionalattachment agent may be utilized to further secure the lens in contactwith the die. For example, the attachment agent may be a resin (e.g., anepoxy resin that may be opaque) in which the device is partiallyimmersed. The resin preferably extends at least slightly (e.g., about0.3 mm or less) above the interface between the die (or the embrittledencapsulant) and the lens in order to further stabilize the lens duringdevice operation and handling. In various embodiments, the attachmentagent may include, consist essentially of, or consist of an opaque resin(and/or other barrier layer) described in U.S. patent application Ser.No. 14/679,655, filed on Apr. 6, 2015 (the '655 application), the entiredisclosure of which is incorporated by reference herein. The attachmentagent and/or barrier layer substantially prevents transmission of UVlight through the majority of such encapsulant, thereby preventingdeterioration and cracking (or other mechanical failure) thereof. Invarious embodiments of the invention, the attachment agent and/orbarrier layer includes, consists essentially of, or consists of aportion of the encapsulant itself that is adjacent to the LED chip andopaque to the UV light emitted by the LED chip. (In such embodiments,the remaining portion of the encapsulant farther away from the LED chipmay also be UV-opaque or transparent, as this more distant encapsulantwill typically not transmit the emitted UV light.) As utilized herein,an “opaque” material substantially does not transmit light of aparticular wavelength or wavelength range (e.g., UV light), and insteadis reflective and/or strongly absorptive (e.g., over a small thickness)to light of the particular wavelength or wavelength range. In otherembodiments of the invention, the barrier layer includes, consistsessentially of, or consists of a solid opaque shield disposed betweenthe LED chip and the encapsulant, which may itself therefore betransparent or opaque to UV light. For example, the shield may becomposed of a metal that is substantially reflective to UV light such asaluminum. In this manner, embodiments of the invention include packagedUV LEDs having long lifetimes, high output power, and high reliability.

In an aspect, embodiments of the invention feature a method ofassembling and burning in an illumination device. A layer of an organicencapsulant is provided over a surface of an ultraviolet (UV)light-emitting semiconductor die. At least a portion of the encapsulantis exposed to UV light to convert at least some of said portion of theencapsulant into non-stoichiometric silica material. Thenon-stoichiometric silica material includes, consists essentially of, orconsists of silicon, oxygen, and carbon. A carbon content of thenon-stoichiometric silica material is greater than 1 ppm and less than40 atomic percent.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The exposure to UV light may precedenominal device operation (i.e., device operation by a customer and/orwithin a larger device, and/or device operation at a current level,operating temperature, and/or oxygen content in the ambient surroundingthe device that are “nominal,” i.e., recommended for normal operationbased on the design and structure of the device). The UV light to whichthe encapsulant is exposed may be emitted by the semiconductor die and,during at least a portion of the exposure, the semiconductor die may beoperated at a current level different from (e.g., higher than or lowerthan) the nominal current level, at an operating temperature differentfrom (e.g., higher than or lower than) the nominal operatingtemperature, and/or within a surrounding ambient containing an oxygencontent different from (e.g., higher than or lower than) the nominaloxygen content. The exposure to UV light may precede packaging of thedevice (e.g., for shipment) and/or shipment to a customer. The exposureto UV light may precede placement of the device within or on a largersystem that utilizes the UV light emitted by the semiconductor die(e.g., for cutting, imaging, disinfection, etc.). The device may emit UVlight at an initial output power before and/or immediately upon exposureof the encapsulant to the UV light, and the output power may decrease toa minimum value (i.e., a value lower than the initial value) and recoverto a final value close to (i.e., approximately 70% to approximately 100%of) the initial value. The encapsulant may be exposed to the UV lightfor at least a time period sufficient for the output power of the deviceto recover to the final value. The exposure of the encapsulant to UVlight may result in the formation of a gaseous byproduct (e.g.,formaldehyde) from the encapsulant and/or the diffusion of the gaseousbyproduct out of the encapsulant. The encapsulant may be exposed to theUV light for at least a time period sufficient for the formation and/ordiffusion of the gaseous byproduct to substantially cease (e.g., beundetectable). The exposure of the encapsulant to UV light may result ina reduction of the carbon content of the encapsulant. The encapsulantmay be exposed to the UV light for at least a time period sufficient forthe carbon content of the encapsulant to drop to approximately 40 atomicpercent or less, approximately 30 atomic percent or less, approximately20 atomic percent or less, approximately 10 atomic percent or less,approximately 5 atomic percent or less, or even approximately 1 atomicpercent or less.

The wavelength of the UV light to which the encapsulant is exposed maybe the same as the wavelength of UV light emitted by the semiconductordie. The wavelength of the UV light to which the encapsulant is exposedmay be different from the wavelength of UV light emitted by thesemiconductor die. The carbon content of the non-stoichiometric silicamaterial may be greater than 1 atomic percent. The carbon content of thenon-stoichiometric silica material may be less than 30 atomic percent,less than 20 atomic percent, less than 10 atomic percent, or even lessthan 5 atomic percent. A rigid lens may be disposed on the encapsulantopposite the semiconductor die. The rigid lens may be inorganic. Therigid lens may include, consist essentially of, or consist of fusedsilica, quartz, and/or sapphire. An attachment material may be disposedaround at least a portion of the semiconductor die and around at least aportion of the rigid lens. The attachment material may include, consistessentially of, or consist of a resin. The attachment material may beopaque to UV light. A top surface of the attachment material may bedisposed above a bottom surface of the rigid lens by no more than 0.5mm. A top surface of the attachment material may be disposed above abottom surface of the rigid lens by no more than 0.3 mm. The rigid lensmay be attached to the semiconductor die via application of a forcesufficient to minimize a thickness of the encapsulant between the rigidlens and the semiconductor die. After attachment of the rigid lens, thethickness of the encapsulant may be insufficient to prevent propagationof thermal expansion mismatch-induced strain between the rigid lens andthe semiconductor die. After attachment of the rigid lens, the thicknessof the encapsulant may be approximately 10 μm or less, approximately 8μm or less, or even approximately 5 μm or less. The rigid lens may be atleast partially hemispherical. The rigid lens may be substantiallyhemispherical. The rigid lens may have a substantially hemisphericalportion and a substantially cylindrical portion disposed thereunder. Therigid lens may be a flat plate. At least a portion of a top surface ofthe rigid lens may be patterned and/or textured to enhance lightemission therefrom.

The encapsulant may include, consist essentially of, or consist ofsilicone before the exposure to UV light. The encapsulant may include,consist essentially of, or consist of silicone oil or silicone resinbefore the exposure to UV light. Before exposure to UV light theencapsulant may have a carbon content greater than 40 atomic percent.After exposure to UV light the non-stoichiometric silica material mayhave a carbon content less than 30 atomic percent. A barrier may bedisposed between the semiconductor die and at least a portion of theencapsulant. The barrier may include, consist essentially of, or consistof a material opaque to UV light. The barrier may include, consistessentially of, or consist of a resin opaque to UV light. The barriermay include, consist essentially of, or consist of a material reflectiveto UV light. The barrier may include, consist essentially of, or consistof aluminum and/or polytetrafluoroethylene. The semiconductor die may bea light-emitting diode die or a laser die. The at least a portion of theencapsulant may be exposed to UV light for a period of approximately 50hours to approximately 500 hours, a period of approximately 100 hours toapproximately 400 hours, a period of approximately 100 hours toapproximately 300 hours, a period of approximately 200 hours toapproximately 300 hours, or a period of approximately 200 hours. The atleast a portion of the encapsulant may be exposed to UV light emitted bythe semiconductor die. At least a portion of the UV light to which theat least a portion of the encapsulant is exposed may be emitted by adevice other than the semiconductor die (e.g., a differentlight-emitting semiconductor die, a UV lamp, etc.). The at least aportion of the encapsulant may be exposed to UV light emitted by boththe semiconductor die and a device other than the semiconductor die. Theat least a portion of the encapsulant may be exposed to UV light havinga wavelength selected from the range of approximately 210 nm toapproximately 280 nm (e.g., approximately 250 nm to approximately 270nm).

In another aspect, embodiments of the invention feature an illuminationdevice that includes or consists essentially of an ultraviolet (UV)light-emitting semiconductor die, a rigid lens for extracting light fromthe light-emitting semiconductor die, and a layer of encapsulantdisposed between the rigid lens and the light-emitting semiconductordie. At least a portion of the layer of encapsulant includes, consistsessentially of, or consists of an organic material converted into anon-stoichiometric silica material by exposure to UV light. Thenon-stoichiometric silica material includes, consists essentially of, orconsists of silicon, oxygen, and carbon. A carbon content of thenon-stoichiometric silica material is greater than 1 ppm and less than40 atomic percent.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The carbon content of thenon-stoichiometric silica material may be greater than 1 atomic percent.The carbon content of the non-stoichiometric silica material may be lessthan 30 atomic percent, less than 20 atomic percent, less than 10 atomicpercent, or even less than 5 atomic percent. The at least a portion ofthe layer of encapsulant may include, consist essentially of, or consistof an organic material converted into a non-stoichiometric silicamaterial by exposure to UV light having a wavelength selected from therange of approximately 210 nm to approximately 280 nm.

In yet another aspect, embodiments of the invention feature anillumination device that includes or consists essentially of anultraviolet (UV) light-emitting semiconductor die, a rigid lens forextracting light from the light-emitting semiconductor die, and a layerof non-stoichiometric silica material disposed between the rigid lensand the light-emitting semiconductor die. The non-stoichiometric silicamaterial includes, consists essentially of, or consists of silicon,oxygen, and carbon. A carbon content of the non-stoichiometric silicamaterial is greater than 1 ppm and less than 40 atomic percent.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The layer of non-stoichiometric silicamaterial may be a portion of and/or disposed within, a layer of anorganic encapsulant (e.g., an encapsulant including, consistingessentially of, or consisting of silicone). The carbon content of thenon-stoichiometric silica material may be greater than 1 atomic percent.The carbon content of the non-stoichiometric silica material may be lessthan 30 atomic percent, less than 20 atomic percent, less than 10 atomicpercent, or even less than 5 atomic percent.

In another aspect, embodiments of the invention feature an illuminationdevice that includes or consists essentially of an ultraviolet (UV)light-emitting semiconductor die, and a layer of encapsulant disposedover and/or around the semiconductor die. At least a portion of thelayer of encapsulant includes, consists essentially of, or consists ofan organic material converted into a non-stoichiometric silica materialby exposure to UV light. The non-stoichiometric silica materialincludes, consists essentially of, or consists of silicon, oxygen, andcarbon. A carbon content of the non-stoichiometric silica material isgreater than 1 ppm and less than 40 atomic percent.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The layer of encapsulant may have theshape of a lens. The carbon content of the non-stoichiometric silicamaterial may be greater than 1 atomic percent. The carbon content of thenon-stoichiometric silica material may be less than 30 atomic percent,less than 20 atomic percent, less than 10 atomic percent, or even lessthan 5 atomic percent. The layer of encapsulant may be disposed over atop surface of the semiconductor die. A barrier material may be disposedproximate a sidewall of the semiconductor die. The barrier material maybe opaque to UV light. The barrier material may include, consistessentially of, or consist of an opaque resin, aluminum, and/orpolytetrafluoroethylene. The at least a portion of the layer ofencapsulant may include, consist essentially of, or consist of anorganic material converted into a non-stoichiometric silica material byexposure to UV light having a wavelength selected from the range ofapproximately 210 nm to approximately 280 nm.

In yet another aspect, embodiments of the invention feature anillumination device that includes or consists essentially of anultraviolet (UV) light-emitting semiconductor die and a layer ofnon-stoichiometric silica material disposed over and/or around thesemiconductor die. The non-stoichiometric silica material includes,consists essentially of, or consists of silicon, oxygen, and carbon. Acarbon content of the non-stoichiometric silica material is greater than1 ppm and less than 40 atomic percent.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The carbon content of thenon-stoichiometric silica material may be greater than 1 atomic percent.The carbon content of the non-stoichiometric silica material may be lessthan 30 atomic percent, less than 20 atomic percent, less than 10 atomicpercent, or even less than 5 atomic percent. The layer ofnon-stoichiometric silica material may be disposed over a top surface ofthe semiconductor die. A barrier material may be disposed proximate asidewall of the semiconductor die. The barrier material may be opaque toUV light. The barrier material may include, consist essentially of, orconsist of an opaque resin, aluminum, and/or polytetrafluoroethylene.

In another aspect, embodiments of the invention feature an illuminationdevice that includes or consists essentially of an ultraviolet (UV)light-emitting semiconductor die and a layer of encapsulant disposedover and/or around the semiconductor die. A first portion of the layerof encapsulant includes, consists essentially of, or consists of anorganic material at least partially converted into a non-stoichiometricsilica material by exposure to UV light. A second portion of the layerof encapsulant includes, consists essentially of, or consists of anorganic encapsulant (e.g., silicone). The non-stoichiometric silicamaterial includes, consists essentially of, or consists of silicon,oxygen, and carbon. A carbon content of the non-stoichiometric silicamaterial is greater than 1 ppm and less than 40 atomic percent.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The first portion of the layer ofencapsulant may include, consist essentially of, or consist of anorganic material at least partially converted into a non-stoichiometricsilica material by exposure to UV light having a wavelength selectedfrom the range of approximately 210 nm to approximately 280 nm. Thecarbon content of the non-stoichiometric silica material may be greaterthan 1 atomic percent. The carbon content of the non-stoichiometricsilica material may be less than 30 atomic percent, less than 20 atomicpercent, less than 10 atomic percent, or even less than 5 atomicpercent. The first portion of the layer of encapsulant may be disposedover a top surface of the semiconductor die. The second portion of thelayer of encapsulant may be disposed proximate a sidewall of thesemiconductor die. The second portion of the layer of encapsulant may bedisposed over the top surface of the semiconductor die and farther awayfrom the top surface of the semiconductor die than the first portion ofthe layer of encapsulant. The first portion of the layer of encapsulantmay be disposed within, and/or at least partially surrounded by, thesecond portion of the layer of encapsulant. A barrier material may bedisposed between the sidewall of the semiconductor die and the secondportion of the layer of encapsulant. The barrier material may be opaqueto UV light. The barrier material may include, consist essentially of,or consist of aluminum, polytetrafluoroethylene, and/or an opaque resin.

In yet another aspect, embodiments of the invention feature anillumination device that includes or consists essentially of anultraviolet (UV) light-emitting semiconductor die and a layer ofencapsulant disposed over and/or around the semiconductor die. A firstportion of the layer of encapsulant includes, consists essentially of,or consists of a non-stoichiometric silica material. A second portion ofthe layer of encapsulant includes, consists essentially of, or consistsof an organic encapsulant (e.g., silicone). The non-stoichiometricsilica material includes, consists essentially of, or consists ofsilicon, oxygen, and carbon. A carbon content of the non-stoichiometricsilica material is greater than 1 ppm and less than 40 atomic percent.

Embodiments of the invention may include one or more of the following inany of a variety of combinations. The carbon content of thenon-stoichiometric silica material may be greater than 1 atomic percent.The carbon content of the non-stoichiometric silica material may be lessthan 30 atomic percent, less than 20 atomic percent, less than 10 atomicpercent, or even less than 5 atomic percent. The first portion of thelayer of encapsulant may be disposed over a top surface of thesemiconductor die. The second portion of the layer of encapsulant may bedisposed proximate a sidewall of the semiconductor die. The secondportion of the layer of encapsulant may be disposed over the top surfaceof the semiconductor die and farther away from the top surface of thesemiconductor die than the first portion of the layer of encapsulant.The first portion of the layer of encapsulant may be disposed within,and/or at least partially surrounded by, the second portion of the layerof encapsulant. A barrier material may be disposed between the sidewallof the semiconductor die and the second portion of the layer ofencapsulant. The barrier material may be opaque to UV light. The barriermaterial may include, consist essentially of, or consist of aluminum,polytetrafluoroethylene, and/or an opaque resin.

These and other objects, along with advantages and features of thepresent invention herein disclosed, will become more apparent throughreference to the following description, the accompanying drawings, andthe claims. Furthermore, it is to be understood that the features of thevarious embodiments described herein are not mutually exclusive and mayexist in various combinations and permutations. As used herein, theterms “substantially” and “approximately” mean±10%, and in someembodiments, ±5%. The term “consists essentially of” means excludingother materials that contribute to function, unless otherwise definedherein. Nonetheless, such other materials may be present, collectivelyor individually, in trace amounts. Herein, the terms “radiation” and“light” are utilized interchangeably unless otherwise indicated.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings, like reference characters generally refer to the sameparts throughout the different views. Also, the drawings are notnecessarily to scale, emphasis instead generally being placed uponillustrating the principles of the invention. In the followingdescription, various embodiments of the present invention are describedwith reference to the following drawings, in which:

FIGS. 1A and 1B depict in cross-section the attachment of a rigid lensto a light-emitting die in accordance with various embodiments of theinvention;

FIG. 1C is a cross-sectional schematic of a light-emitting deviceincorporating a rigid lens in the form of a flat plate;

FIG. 1D is a cross-sectional schematic of a light-emitting deviceincorporating a rigid lens in the form of a textured flat plate;

FIG. 2A is a schematic cross-section of, at room temperature, anillumination device incorporating a light-emitting die, an encapsulant,and a rigid lens in accordance with various embodiments of theinvention;

FIG. 2B is a magnified representation of the stress state within theencapsulant of FIG. 2A;

FIG. 3A is a schematic cross-section of, at elevated temperature, anillumination device incorporating a light-emitting die, an encapsulant,and a rigid lens in accordance with various embodiments of theinvention;

FIG. 3B is a magnified representation of the stress state within theencapsulant of FIG. 3A;

FIG. 4A is a schematic cross-section of a light-emitting die utilized inembodiments of the invention;

FIG. 4B depicts the light-emitting die of FIG. 4A after substratethickness reduction and texturing performed in accordance withembodiments of the invention;

FIG. 5 depicts plots of the light intensity emitted from a UV LED withand without a rigid lens applied thereto in accordance with embodimentsof the invention;

FIG. 6 depicts plots of far filed patterns of light-emitting dies withand without a rigid lens applied thereto in accordance with embodimentsof the invention;

FIG. 7 is a schematic depiction of the effect of lens size on thedistortion of light from a light-emitting die attached thereto inaccordance with embodiments of the invention;

FIG. 8 is a schematic cross-section of a lens having hemispherical andcylindrical portions attached to a light-emitting die in accordance withvarious embodiments of the invention;

FIG. 9 is a table of photon extraction efficiencies and far fieldpatterns as functions of lens dimensions and encapsulant thickness forvarious embodiments of the invention;

FIG. 10 is a graph of relative output power for a UV light-emittingdevice over time in accordance with various embodiments of theinvention;

FIG. 11A depicts an exemplary photochemical reaction occurring inorganic encapsulant materials in accordance with various embodiments ofthe invention;

FIG. 11B is a schematic partial cross-section of a device during thephotochemical reaction of FIG. 11A in accordance with variousembodiments of the invention;

FIG. 11C is a schematic partial cross-section of a device after thephotochemical reaction of FIG. 11A in accordance with variousembodiments of the invention;

FIG. 12 is a graph of micro-infrared spectroscopy characterizationresults of an encapsulant before exposure to UV light (0 hours) andafter exposure times of 48 hours and 1300 hours in accordance withvarious embodiments of the invention;

FIG. 13A is a graph of energy-dispersive X-ray (EDX) spectroscopymeasurements of an encapsulant prior to exposure to UV light inaccordance with embodiments of the invention;

FIG. 13B is a graph of energy-dispersive X-ray (EDX) spectroscopymeasurements of an encapsulant after exposure to UV light for 48 hoursin accordance with embodiments of the invention;

FIG. 13C is a graph of energy-dispersive X-ray (EDX) spectroscopymeasurements of an encapsulant after exposure to UV light for 200 hoursin accordance with embodiments of the invention;

FIG. 13D is a graph of energy-dispersive X-ray (EDX) spectroscopymeasurements of an encapsulant after exposure to UV light for 1300 hoursin accordance with embodiments of the invention;

FIG. 14 is a graph of the approximate compositions of the encapsulantsof FIGS. 13A-13D;

FIGS. 15A-15C are schematic cross-sections of devices incorporatingencapsulants converted into non-stoichiometric silica material inaccordance with various embodiments of the invention;

FIG. 15D is a schematic cross-section of a device incorporating anencapsulant converted into non-stoichiometric silica material, as wellas unconverted encapsulant and/or barrier materials, in accordance withvarious embodiments of the invention;

FIGS. 15E and 15F are schematic cross-sections of devices incorporatingencapsulants converted into non-stoichiometric silica material inaccordance with various embodiments of the invention;

FIG. 15G is a schematic cross-section of a device incorporating anencapsulant converted into non-stoichiometric silica material, as wellas unconverted encapsulant and/or barrier materials, in accordance withvarious embodiments of the invention;

FIG. 15H is a schematic cross-section of a device incorporating anencapsulant converted into non-stoichiometric silica material inaccordance with various embodiments of the invention; and

FIG. 16 is a schematic cross-section of a device incorporating a rigidlens and an attachment material in accordance with various embodimentsof the invention.

DETAILED DESCRIPTION

Embodiments of the invention include approaches to increase thephoton-extraction efficiency of light-emitting devices such as UV LEDsby minimizing the total internal reflection of light transmitted fromsubstrate into the surrounding ambient. The technique uses a thin layer(e.g., approximately 10 μm, or even thinner) of an encapsulant (e.g., anepoxy) that is transparent to short-wavelength UV radiation. FIG. 1Adepicts a semiconductor die 100 having an encapsulant 110 disposed on asurface 120 thereof, as well as a lens 130 that will be attached to die100 via the encapsulant 110. In some embodiments, the encapsulant 110 isapplied to surface 140 of the lens 130 instead of or in addition tosurface 120 of the die 100 prior to attachment of die 100 to lens 130.

The semiconductor die 100 may include or consist essentially of alight-emitting device such as an LED or a laser. In various embodiments,die 100 emits UV light, e.g., UVC light. The light-emitting die 100 mayinclude an AlN substrate and, thereover, one or more quantum wellsand/or strained layers including or consisting essentially of AlN, GaN,InN, or any binary or tertiary alloy thereof, within an “active,”light-emitting region of the die 100. In various embodiments, die 100includes a substrate and/or device structure resembling those detailedin U.S. Pat. No. 7,638,346, filed on Aug. 14, 2006, U.S. Pat. No.8,080,833, filed on Apr. 21, 2010, and/or U.S. Patent ApplicationPublication No. 2014/0264263, filed on Mar. 13, 2014, the entiredisclosure of each of which is incorporated by reference herein.

The encapsulant 110 may be organic and/or polymeric. In variousembodiments of the invention, the encapsulant 110 is silicone-based, andmay include, consist essentially of, or consist of, for example, asilicone oil and/or a silicone resin. Prior to attachment of the lens130, the surface 120 of the die 100 may be treated, e.g., roughened,textured, and/or patterned, in order to maximize the light extractiontherefrom (i.e., by increasing the critical angle for escape of thelight), as described in U.S. Ser. No. 12/764,584, filed on Apr. 21,2010, the entire disclosure of which is incorporated by referenceherein.

As shown in FIG. 1B, the lens 130 is attached to die 100 via theencapsulant 110 (which may also have adhesive properties). The lens 130is typically rigid and, in various embodiments, is at least partiallyhemispherical in shape. Lens 130 may be substantially hemispherical, asshown in FIGS. 1A and 1B, or may be composed of a substantiallyhemispherical portion and a substantially cylindrical portion (asdescribed below). In some embodiments the lens 130 includes, consistsessentially of, or consists of a substantially flat plate, as shown inFIG. 1C, or a flat plate having a surface that has been patterned ortextured to improve light extraction therefrom, as shown in FIG. 1D. Thelens 130 is typically inorganic, and may include, consist essentiallyof, or consist of, for example, fused silica, quartz, and/or sapphire.In some embodiments, the encapsulant 110 is heated (e.g., toapproximately 60° C.) to provide enough fluidity to substantiallygaplessly form an interface between lens 130 and die 100. Typically, theencapsulant 110 is heated at a temperature at which it still hassufficient viscosity to enable proper positioning of the lens 130 on thedie 100, even after contact therebetween. (Liquid encapsulants such assilicone oil may be applied at room temperature, at least in someembodiments.) In some embodiments, force (represented by arrows 150 inFIG. 1B) is applied to the die 100 and/or the lens 130 in order tominimize the space therebetween, and thus also minimize the thickness ofthe encapsulant 110 therein. Even in embodiments in which theencapsulant 110 degrades (due to, e.g., exposure to UV light from die100), the thin thickness of the layer may prevent catastrophicdegradation of the performance of the device. After the lens 130 ispositioned on die 100, the entire structure may be raised to an evenhigher temperature (e.g., up to approximately 150° C. to approximately170° C. for 0.5 hour to 2 hours) to cure the encapsulant 110 andsolidify the attachment of the lens 130 to the die 100.

The encapsulant 110 may be, in some embodiments, at least partiallycured before the lens 130 is positioned on the die 100. For example, theencapsulant (e.g., dispensed on the lens 130 and/or the die 100) may beheated to, for example, up to approximately 150° C. to approximately170° C. for 0.5 hour to 1 hour.

Various embodiments of the present invention utilize thin layers of theencapsulant material in order to ameliorate the effects of thedeterioration of such layers, at least during initial periods ofexposure to UV light. For example, particularly for high-power LEDs,various embodiments of the invention utilize layers of encapsulanthaving thicknesses less than approximately 10 μm, as detailed in U.S.patent application Ser. No. 13/533,093, filed on Jul. 19, 2012, theentire disclosure of which is incorporated by reference herein.

In various embodiments, the device (including, e.g., the die 100,encapsulant 110, and lens 130) may be subjected to a vacuum before,during, and/or after the curing of the encapsulant 110 in order topromote removal of any air and/or bubbles trapped in and/or proximatethe encapsulant 110. For example, the device may be placed within avacuum oven under, e.g., 10 Torr of vacuum. The vacuum may be applied atroom temperature (e.g., approximately 25° C.) or, if the encapsulant 110is being at least partially cured simultaneously, the vacuum may beapplied at the curing temperature (e.g., as described above) or at anintermediate temperature between room temperature and the curingtemperature. The vacuum may be applied for a time period of, forexample, approximately 5 minutes to approximately 20 minutes, or thevacuum may be applied for the curing time (e.g., as described above) orfor an intermediate time between approximately 5 minutes and the curingtime.

In various embodiments, the lifetime of the overall device (i.e., thesemiconductor die with the rigid lens attached) is improved by makingthe encapsulant layer as thin as possible. Such thickness minimizationmay be achieved by applying force to the lens and/or the die during thecuring process. The minimization of encapsulant thickness typicallyrenders the encapsulant thickness insufficient for the encapsulant tofunction as a thermal expansion mismatch buffer (in which case one wouldtypically increase the encapsulant thickness to prevent strainpropagation therethrough and improve reliability of the device). FIGS.2A, 2B, 3A, and 3B depict the impact of temperature change (resultingfrom, e.g., the elevated temperature of the die during light emission)on the strain profile within the assembled device in accordance withvarious embodiments of the present invention.

FIGS. 2A and 2B depict an assembled device and the strain state of theencapsulant 110 at approximately room temperature (e.g., after assemblybut while die 100 is not operating). As shown, since the device is atapproximately the temperature at which it was assembled, there isapproximately no thermal-mismatch strain resulting from and/orpropagating between the die 100 and the lens 130, despite the fact thattheir expansions of thermal expansion are different. FIG. 2B indicatesthat, in this situation, there is substantially no shear stress withinthe encapsulant 110 indicative of such thermal-mismatch strain.

In contrast, FIGS. 3A and 3B depict the assembled device and the strainstate of the encapsulant 110 at elevated temperature (e.g., duringoperation of die 100). As shown, the difference in thermal-expansioncoefficients of the lens 130 and the die 100 results in thermal-mismatchstrain propagating therebetween, as indicated by the shear stress anddeformation through the entirety of the layer of encapsulant 110.Specifically, in this case the thickness of the encapsulant 110 isinsufficient to accommodate the thermal mismatch-induced strain andprevent its propagation between die 100 and lens 130. (In the contrarycase where the thickness of the encapsulant is sufficiently thick, atleast a portion of the encapsulant layer would greatly resemble theencapsulant 110 shown in FIG. 2B, as the shear stress within the layerwould be proportionally smaller.) The linear thermal expansioncoefficient of die 100 may be larger than that of the lens 130, forexample, larger by approximately a factor of 10 or more. In oneembodiment, die 100 (or at least a substrate portion thereof supportingone or more active, light-emitting layers) includes or consistsessentially of single-crystal AlN and has a linear thermal expansioncoefficient of approximately 5×10⁻⁶/K, while lens 130 includes, consistsessentially of, or consists of silica and has a linear thermal expansioncoefficient of approximately 0.6×10⁻⁶/K. Despite the amount of shearstress through the entire thickness of the encapsulant 110, and thus theamount of thermal expansion mismatch-induced strain propagating betweenlens 130 and die 100, the optical performance of the assembled device issurprisingly superior due to the minimized thickness of the encapsulant110, which limits the decrease in optical transmission due tolight-induced deterioration of encapsulant 110.

The impact of the thermal-mismatch strain may be decreased via reductionof the thickness of die 100 by, e.g., removal of at least a portion ofthe substrate, on which the light-emitting layers are formed, thereof.Such thinning may be performed in addition to, or in conjunction with,the surface patterning described above with reference to FIGS. 1A and1B, as described in U.S. Pat. No. 8,080,833, filed Apr. 21, 2010, theentire disclosure of which is incorporated by reference herein. FIG. 4Aschematically depicts a semiconductor die 100 that incorporates asubstrate 600 and, thereover, a layered region 610 that includes orconsists essentially of one or more epitaxially deposited semiconductorlayers including the active (i.e., light-emitting) region of die 100.The substrate 600 is typically a semiconductor material, e.g., silicon,GaN, GaAs, InP, or AlN, but in various embodiments includes, consistsessentially of, or consists of single-crystal AlN. In embodiments inwhich die 100 is a light-emitting device, layered region 610 typicallyincludes one or more of buffer layers, cap layers, contact layers,quantum wells, multiple quantum well (MQW) regions (i.e., multiplequantum wells separated by thin barrier layers), as known to those ofskill in the art.

In order to mitigate the impact of thermal-mismatch strain on die 100and enhance light transmission from die 100, at least a portion ofsubstrate 600 may be removed and/or textured, as shown in FIG. 4B. If,for example, substrate 600 has a total thickness variation higher thanabout 20 μm, then the back surface 120 may be ground, for example, witha 600 to 1800 grit wheel. The removal rate of this step may bepurposefully maintained at a low level (approximately 0.3-0.4 μm/s) inorder to avoid damaging the substrate 600 or the layered region 610.After the optional grinding step, the back surface 120 may be polishedwith a polishing slurry, e.g., a solution of equal parts of distilledwater and a commercial colloidal suspension of silica in a bufferedsolution of KOH and water. The removal rate of this step may varybetween approximately 10 μm/min and approximately 15 μm/min. Substrate600 may be thinned down to a thickness of approximately 200 μm toapproximately 250 μm, or even to a thickness of approximately 20 μm toapproximately 50 μm, although the scope of the invention is not limitedby this range. In other embodiments, the substrate 600 is thinned toapproximately 20 μm or less, or even substantially completely removed.The thinning step may be followed by wafer cleaning in, e.g., one ormore organic solvents. In one embodiment of the invention, the cleaningstep includes immersion of substrate 600 in boiling acetone forapproximately 10 minutes, followed by immersion in boiling methanol forapproximately 10 minutes.

Once substrate 600 is cleaned, the surface 120 thereof may be patterned,i.e., textured, by etching in a suitable solution (e.g., a basicsolution such as KOH in deionized (DI) water). In another embodiment ofthe invention, the etching agent is a solution of NaOH in DI water. Themolarity of the basic solution may vary between approximately 1M andapproximately 20M, and the etching time may vary between approximately 1minute and approximately 60 minutes. The temperature of the etchingsolution may vary between approximately room temperature up toapproximately 100° C. Similar results may be obtained when using ahigher molarity solution for shorter periods of time and vice versa. Inone embodiment of the invention, substrate 600 is etched in a 4Msolution of KOH and DI water for 8 minutes while maintaining thesolution at approximately 20° C.

The rigid lens 130 may be formed in the desired shape and size from alarger piece of the desired material or may be directly “molded” intothe desired shape and size. For example, in accordance with variousembodiments of the invention, a sol-gel process is utilized to form thelens 130. For example, in order to produce a fused-silica lens, aprecursor chemical solution containing nano-scaled silica particles maybe inserted into a mold where it thickens into a gel. The thickened partis then removed from the mold and dried, resulting in an open-porematerial having pores that may be filled with a gas. The dried part isthen sintered at temperatures of, for example, greater than 1000° C.,during which the part shrinks to the desired dimensions and densifiesinto a material nearly identical to fused silica and with hightransparency in the deep UV. The lens 130 may contain trace amounts ofcarbon or other elements from, e.g., the precursor solution.Designations for lenses herein such as “fused silica” and the like alsoencompass such materials formed by solution processing (such as sol-gelprocesses), even if such materials also contain trace elements such ascarbon (although in various embodiments of the present invention, lenses130 have carbon contents less than 1 ppm). Moldable processes such assol-gel processes enable the tuning of exact dimensions and shape withhigh reproducibility and low cost when producing rigid lenses such asthe fused-silica lenses described above.

Due to the larger refractive index of the encapsulant 110 (e.g., around1.4 at 260 nm) compared to the air, the critical angle calculated fromSnell's law for total internal reflection from the substrate 600 (e.g.,AlN) into the encapsulant 110 is increased, which in turn increases thephoton-extraction efficiency of the device. The lens 130 then extractssubstantially all of the light from the encapsulant 110, as the lens 130may have a similar refractive index (e.g., around 1.5 at 260 nm). Thelens 130 is also typically larger in size than the die 100 (e.g., alonga lateral dimension such as a width or diameter) in order to extract asmuch light as possible from the die 100. In an embodiment, the die 100is approximately 0.8 mm on a side, and the lens 130 is hemisphericalwith a diameter of approximately 2 mm. As shown in FIG. 5, the outputpower of an exemplary UV LED is increased by approximately 2.6× with theaddition of a hemispherical fused silica lens 130 attached to the die100 with a thin layer of an encapsulant 110. FIG. 5 includes plots, asfunctions of wavelength, of the intensity 700 of light emitted withoutthe lens 130 and the intensity 710 of light emitted with the lens 130.

The radiation pattern of a light-emitting semiconductor die 100, e.g.,an LED, may also be improved via selection of the inorganic lensmaterial and shape of its surface. FIG. 6 depicts the full width,half-maximum (FWHM) of the radiation pattern from an LED both with andwithout a sapphire lens attached to the LED die 100 with a thin layer ofencapsulant 110. As shown, the far field pattern 800 of the LED die 100without lens 130 has a FWHM of approximately 120°, while with thesapphire lens 130, the far field pattern 810 has a FWHM of approximately72°. The far field pattern may be reduced even further via use of acylindrical-hemispherical lens, as detailed below.

Typically, the radiation pattern emitted by an LED after attachment of ahemispherical lens will remain Lambertian (as shown in FIG. 6) afterattachment of the lens if the encapsulant is kept very thin. However,the size of the emitting surface will generally be magnified by theaddition of the lens. The amount of this magnification will be equal tothe index of refraction of the lens and the distortion of the LED willbe reduced by making the lens diameter larger relative to the size ofthe LED. That is (and as shown in FIG. 7),

$\begin{matrix}{\frac{X_{2}}{X_{1}} = {\frac{\frac{r*\sin \; \theta_{2}}{\cos \left( {\theta_{2} - \theta_{1}} \right)}}{r*\sin \; \theta_{1}} = \frac{n}{\cos \left( {\theta_{2} - \theta_{1}} \right)}}} & (1) \\{{\sin \; \theta_{2}} = {n*\sin \; \theta_{1}}} & (2) \\{\frac{X_{3}}{X_{1}} = {\frac{\frac{r}{\tan \; \theta_{4}}}{\frac{r}{\tan \; \theta_{3}}} = \frac{n}{\frac{\cos \; \theta_{4}}{\cos \; \theta_{3}}}}} & (3) \\{{\sin \; \theta_{4}} = {n*\sin \; \theta_{3}}} & (4)\end{matrix}$

where a ray 900 is a light ray emitted from a point 920 on the LED 100in the direction perpendicular to the flat surface 920 of hemisphericallens 130; X₁ is the distance between point 920 and center point 930 ofthe LED 100; X₂ is the distance between the point 940, where the reverseextending line of ray 900's emergent ray intersects with the flatsurface 920, and center point 930; r is the radius of hemispherical lens130; θ₁ is the incident angle of ray 900; θ₂ is the transmission angleof ray 900; n is the refractive index of the hemispherical lens 130; ray950 is a light ray emitted from point 910 through the point directlyabove center point 930; X₃ is the distance between the point 960, wherethe reverse extending line of ray 950's emergent ray intersects with theflat surface of hemispherical lens 130, and center point 930; θ₃ is theincident angle of ray 950; and θ₄ is the transmission angle of ray 950.

As indicated by equations (1) and (3) above, when X₁ is much smallerthan r, X₂/X₁ and X₃/X₁ both converge to n and the two reserve extendedlines intersect almost at the same point on the flat surface of lens130. For dies 100 with an edge length (or diameter, for circular dies)comparable to twice the radius r (i.e., the diameter) of the lens 130,the image of (and thus the light emitted from) die 100 is distorted.Thus, in various embodiments of the invention, the diameter of lens 130is significantly larger (e.g., at least two times larger, five timeslarger, or even ten times larger or more) than an edge length ordiameter of die 100 to minimize distortion of light from die 100.

The far field divergence of the die 100 (e.g., an LED) is improved withlittle or no impact on photon extraction efficiency in accordance withvarious embodiments of the present invention via the use of a lens 130having a shape with a cylindrical component as well as a hemisphericalcomponent, as shown in FIGS. 8 and 9. FIG. 8 depicts an LED die 100(e.g., a mid-UV LED) having a roughened (i.e., textured) surface 120 andattached to such a lens 130 via a thin layer of encapsulant 110 (e.g., asilicone-based encapsulant). As shown, the lens 130 has a hemisphericalportion 1000 and a cylindrical portion 1010 (e.g., having a constantdiameter equal to that of the largest diameter of hemispherical portion1000) having a thickness, or “cylinder height” 1020. Simulations wereperformed to determine the photon extraction efficiency and far fielddivergence of various different embodiments. The results are compared toa baseline value of photon extraction efficiency for a bare (butroughened) LED without the lens 130 or encapsulant 110, shown as Case 1in FIG. 9. Cases 2 and 3 represent embodiments in which the lens 130 ispurely hemispherical (i.e., no cylindrical component), demonstrating theabove-described increase in photon extraction efficiency and modestimprovement in the far field divergence. As FIG. 9 illustrates,increasing the thickness of the cylindrical component of the lensenables the decrease of far field divergence to at least 40° FWHM withlittle or no deleterious effect on the photon extraction efficiency, andto even lower levels (i.e., to at least 25°) with only modest impact onthe photon extraction efficiency (which remains much improved over thatof the Case 1 baseline value). This nearly collimated beam of UV lightis very desirable for certain applications that utilize a concentratedbeam. As also shown in FIG. 9, increases in the lens diameter also tendto improve photon extraction efficiency and to decrease the far fielddivergence, as also discussed above.

In addition to improving the light extraction efficiency of a singlesemiconductor die, embodiments of the invention exhibit similar resultswhen utilizing an array of two or more semiconductor dies (e.g., LEDdies). For example, a 4×4 array of dies may be used with a rigid lenshaving a diameter that is significantly larger (e.g., at least two timeslarger, five times larger, or even ten times larger or more) than anedge length or diameter of the array to minimize distortion of light.Modeling was performed for arrays of different sizes (i.e., differentnumbers of dies) and showed that a relatively larger diameter of thelens compared to the edge length or diameter of a full array may benecessary to achieve similar improvement of the photon extractionefficiency compared to embodiments incorporating a single smallsemiconductor die. The modeling results are shown in the table below.

Edge Lens Photon Far Size of Lengths of Lens Di- Extraction Field LEDarray the Array Material ameter Efficiency FWHM 1 × 1 0.8 × 0.8 mm N/AN/A 1.0x 120° 1 × 1 0.8 × 0.8 mm Fused Silica  2 mm 2.2x 114° 3 × 3 3.8× 3.4 mm Fused Silica  6 mm 1.9x 140° 3 × 3 3.8 × 3.4 mm Fused Silica  8mm 2.2x 134° 4 × 4 5.3 × 4.7 mm Fused Silica  8 mm 1.9x 144° 4 × 4 5.3 ×4.7 mm Fused Silica 10 mm 2.2x 140° 5 × 5 6.8 × 6.0 mm Fused Silica 10mm 1.9x 144° 5 × 5 6.8 × 6.0 mm Fused Silica 14 mm 2.2x 134°

In addition, a 3×3 array of light-emitting semiconductor dies wasintegrated with a 6 mm diameter rigid lens and exhibited an improvementof light extraction efficiency of 1.4×, even though the lens was notlarge enough to fully optimize the photon extraction efficiency.Therefore, embodiments of the invention incorporating even larger lenseswill exhibit improvements in photon extraction efficiency of 2× or evenmore.

Various embodiments of the invention incorporate an organic encapsulantthat degrades upon exposure to UV light, such as a silicone oil orsilicone resin. In particular, such organic encapsulants may experiencepartial oxidation when exposed to UV light (e.g., during an initialperiod of light emission by the device), altering the refractive indexof the encapsulant and/or forming small localized areas from which lightfrom the light-emitting die scatters, decreasing the amount of UV lightreaching the lens and ultimately being emitted therefrom. In accordancewith various embodiments of the invention, such encapsulants aresurprisingly and advantageously at least partially converted tonon-stoichiometric silica material via additional exposure to UV lightduring a burn-in period before final packaging, shipment to a customer,and/or incorporation of the UV device into a larger system or deviceadvantageously utilizing the emitted UV light (e.g., a disinfection,purification, and/or biocidal system for liquids and/or gases, medicaldevices, imaging systems, curing systems, printing systems, opticalsensors, etc.). Specifically, the carbon content of the encapsulantdiminishes to, for example, less than 40 atomic %, less than 30 atomic%, or even less than 20 atomic % as the encapsulant is at leastpartially converted into the non-stoichiometric silica material, and thetransmissivity of the encapsulant improves considerably and is robustfor at least thousands of hours of operation of the device. In variousembodiments, after exposure to UV light, the encapsulant is convertedinto a non-stoichiometric silica material consisting essentially of, oreven consisting of, carbon, oxygen, and silicon, where the carboncontent is greater than 1 ppm (and in some cases greater than 1 atomic%) and less than 30 atomic %, or even less than 20 atomic %. In suchembodiments, the preference for a small encapsulant thickness detailedabove may be relaxed, and the encapsulant may have a thickness greaterthan 10 μm (or even greater than 50 μm) and/or may even be utilized toreplace the rigid lens 130.

FIG. 10 is a graph of relative output power for a UV light-emittingdevice in accordance with embodiments of the present invention thatincorporates the encapsulant conversion process described above. Asshown, when the encapsulant is initially exposed to UV light from thedevice during a burn-in period 1000 (i.e., within the manufacturingprocess before final packaging and shipment to a customer), the outputpower drops dramatically for a period of less than 200 hours. Then,after continued exposure to the UV light, the output power graduallyrises to a level nearly as high as the initial output power (e.g., toabout 80%-90% of the brief initial power level) after a period of200-400 hours, and then the output power remains substantially constantwith device operation time during a customer operation period 1010 up toat least a period of 2000 hours. As shown in FIG. 10, the initialoutput-power drop generally corresponds to a “burn-in” process duringdevice manufacturing and before sales of devices to customers; thus,once such devices are provided to customers they exhibit no suchdramatic drop in output power with usage. The data shown in FIG. 10 isfor exposure to UV light having a wavelength of approximately 263 nm,although embodiments of the present invention are not limited to thisparticular wavelength and may utilize any wavelength of UV light (e.g.,UVC light).

FIG. 11A illustrates a photochemical reaction that the encapsulant maybe undergoing in various embodiments of the present invention. As shown,the encapsulant may be a silicone oil, i.e., a liquid polymerizedsiloxane with organic side chains. The encapsulant is exposed to theenergetic UV photons from the light-emitting die, and the encapsulant isgradually converted into non-stoichiometric silica material (andeventually even silica) and water via intermediate conversion ofcarbon-containing side chains into hydroxyl side chains. As shown inFIG. 11B, during the conversion process small portions of theencapsulant 110 may thus be converted into material having a differentrefractive index, thereby forming scattering centers 1100 and leading toscattering events that diminish the output power of the device duringthe burn-in process implemented during device manufacturing. Once asubstantial portion, or even all, of the encapsulant 110 is convertedinto non-stoichiometric silica material 1110 (or eventually evensilica), as shown in FIG. 11C, the number of scattering events isreduced or substantially eliminated, and the output power recovers tohigh levels as shown in FIG. 10.

FIG. 12 shows micro-infrared spectroscopy characterization results of anencapsulant in accordance with embodiments of the present inventionbefore exposure to UV light (0 hours) and after exposure times of 48hours and 1300 hours. In FIG. 12, the sample exposed for 48 hours wasexposed to UV light having a wavelength of 257 nm, and the sampleexposed for 1300 hours was exposed to UV light having a wavelength of263 nm; these wavelengths are not limiting, and embodiments of theinvention may utilize other wavelengths of UV light. As shown, the peaksarising from the alkyl groups Si—CH₃ and C—H largely disappear betweenthe exposure times of 48 hours and 1300 hours, while peaks for O—H andH₂O appear during that time. Notably, the spectroscopy profile of thesample after 1300 hours closely approximates that of pure silica. Inaddition, as indicated on FIG. 12, the output power (“Ptx”) of thesample exposed for 1300 recovered to about 72% of the initial powerlevel (i.e., at 0 hours), much higher than the 58% of the initial powerlevel exhibited by the sample exposed for 48 hours.

FIGS. 13A-13D depict confirmatory results from energy-dispersive X-ray(EDX) spectroscopy measurements of an encapsulant in accordance withembodiments of the present invention at exposure times of 0 hours, 48hours, 200 hours, and 1300 hours, respectively. As shown, the amount ofcarbon detected in the encapsulant decreases with increasing UV exposuretime, while the amount of oxygen increases. FIG. 13A depicts the resultsfrom the unconverted encapsulant prior to any exposure to UV light andhaving an initial power output. As shown in FIG. 13B, after an exposureto UV light of 48 hours, the carbon content of the encapsulant hasdropped, the oxygen content has increased, and the power output level isonly about 60% of the initial power output due to, e.g., theabove-described scattering from localized regions of the encapsulanthaving different refractive indices. FIG. 13C shows the EDX spectroscopymeasurements at the approximate end of the burn-in period after exposureto UV light of 200 hours. As shown, the carbon content of theencapsulant has decreased dramatically as substantially all of theencapsulant has been converted into non-stoichiometric silica material,and the output power has recovered to approximately the same level asthat exhibited prior to any exposure to UV light. FIG. 13D shows that,after exposure to UV light for 1300 hours, the carbon content hasfurther decreased (with concomitant increase in oxygen content), as thenon-stoichiometric silica material continues to be converted intonon-stoichiometric silica material having a lower carbon content, andthence (i.e., after even more exposure to UV light) into substantiallypure silica. The output power level after 1300 hours has stabilized atan intermediate level (in the depicted embodiment, 73%) higher than thatexhibited during the burn-in procedure but lower than that exhibited bythe device at initial power-on.

FIG. 14 plots the approximate composition of the encapsulant of FIGS.13A-13D as a function of device operation (and thus UV exposure) time.As shown, as the device operation time approaches 1300 hours, the amountof oxygen increases, the amount of silicon slightly increases, and theamount of carbon diminishes. Notably, after 1300 hours, the oxygencontent approaches the approximately 67% of pure silica while thesilicon content approaches the 33% of pure silica. In FIGS. 13A-13D and14, the sample exposed for 48 hours was exposed to UV light having awavelength of 257 nm, the sample exposed for 200 hours was exposed to UVlight having a wavelength of 279 nm, and the sample exposed for 1300hours was exposed to UV light having a wavelength of 263 nm; thesewavelengths are not limiting, and embodiments of the invention mayutilize other wavelengths of UV light.

In some embodiments, particularly those in which the encapsulant haslarger thicknesses, only the portion of the encapsulant closest to thelight-emitting die is partially or substantially converted intonon-stoichiometric silica material, leaving a second portion (closer tothe rigid lens) substantially unconverted. In some embodiments, theencapsulant is exposed to UV light from sources other than thelight-emitting die of the device in addition to or instead of the UVlight from the light-emitting die. For example, UV light from other UVLEDs or UV lamps may be shone on the encapsulant from above, enhancingthe conversion of the encapsulant into non-stoichiometric silicamaterial and/or converting additional region(s) of the encapsulant intonon-stoichiometric silica material.

FIGS. 15A-15H depict UV light-emitting devices in accordance withvarious embodiments of the present invention. In each figure, the die100 is topped with an encapsulant 1500 that has been partially orsubstantially fully converted into non-stoichiometric silica materialvia exposure to UV light. Various embodiments also incorporate a lens130 as described above. The converted encapsulant 1500 typicallycontains carbon at levels greater than 1 ppm (or even greater thanapproximately 1 atomic %) but less than approximately 40 atomic %, lessthan approximately 30 atomic %, or even less than approximately 20atomic %. As mentioned above, the lens 130 typically contains less than1 ppm of carbon, or is substantially free of carbon. As shown in FIG.15B, the encapsulant 1500 may be shaped into a lens shape and thus beutilized to replace the lens 130 present in some embodiments of theinvention (see, e.g., FIG. 15A). As shown in FIG. 15C, the lens 130(whether having a rounded shape or taking the form of a flat plate) doesnot necessarily overhang the sides of the die 100. In addition, aspreviously shown in FIGS. 1C and 1D, the lens 130 may include, consistessentially of, or consist of a flat plate that may be larger than thedie (and thus, e.g., overhangs the die on at least one side) and thathas been patterned or roughened to assist with photon extraction, forinstance, a Fresnel lens.

FIG. 15D depicts an embodiment of the present invention in which theconverted encapsulant 1500 and the lens 130 are disposed above the topsurface of the die 100, while regions 1510 proximate the sides of die100 may include, consist essentially of, or consist of unconvertedencapsulant (i.e., encapsulant not exposed to UV light or exposed to UVlight of insufficient power and/or duration to convert an appreciableamount of the encapsulant into non-stoichiometric silica material)and/or a barrier material that is opaque or reflective to the UV lightemitted by die 100. For example, a barrier (e.g., a barrier including,consisting essentially of, or consisting of Al and/or anotherUV-reflective material such as polytetrafluoroethylene (PTFE)) may bedisposed between the sidewalls of the die 100 and the remaining portionsof regions 1510 (as detailed in the '655 application), which are thusshielded from appreciable exposure to UV light emitted by die 100 andremain unconverted.

As shown in FIGS. 15E and 15F, the converted encapsulant 1500 may beshaped (e.g., by molding) into various shapes (e.g., a hemisphericallens or a flat plate) before or after it is disposed on the die 100. Forexample, in some embodiments the encapsulant is molded into a desiredshape and exposed to UV light before it is attached to the die 100. FIG.15H depicts an embodiment in which the converted encapsulant has acurved top surface and otherwise conforms to the top surface of the die100. FIG. 15G is similar to FIG. 15D, but the lens 130 has been replacedby a region including, consisting essentially of, or consisting of theconverted encapsulant 1500. As shown, the device may still incorporateregions 1510 that include, consist essentially of, or consist ofunconverted encapsulant and/or a barrier to UV light. As detailed above,one or more barrier materials may separate the die 100 from theunconverted regions 1510.

In some embodiments, the conversion of the encapsulant embrittles theconverted encapsulant 1500, and thus the lens 130 may be more likely toloosen or become detached from the light-emitting die 100. In suchembodiments, an additional attachment agent or attachment material 1600may be utilized to further secure the lens in contact with the die, asshown in FIG. 16. For example, the attachment agent 1600 may be a resin(e.g., an epoxy resin that may be opaque) in which the device ispartially immersed. In other embodiments, the attachment agent 1600includes or consists essentially of a clamp or other mechanical fastenerthat maintains contact between the lens 130 and the die 100 (or theembrittled encapsulant 1510). The attachment agent 1600 may extend atleast slightly (e.g., approximately 0.5 mm or less, or approximately 0.3mm or less, or approximately 0.1 mm or less) above the interface betweenthe die 100 (or the embrittled encapsulant 1510) and the lens 130 inorder to further stabilize the lens during device operation andhandling. The thin layer of converted encapsulant 1510 between the die100 and the lens 130 is omitted from FIG. 16 for clarity. In variousembodiments, the attachment agent 1600 does not extend appreciably(e.g., not by more than 0.5 mm) above the bottom surface of the lens 130so as not to block emission of UV light from the device anddeleteriously impact output power of the device.

In various embodiments of the invention, after the burn-in periodexposing the organic encapsulant to UV light (i.e., from thelight-emitting die itself and/or from a secondary, extrinsic sourceother than the die, for a time period of, e.g., approximately 100 toapproximately 300 hours), any remaining portion of the manufacturingprocess of the UV device is completed and the device may be shipped to acustomer and/or incorporated into a larger system or device thatutilizes the UV light emitted by the light-emitting die. For example,the UV device may be subjected to quality-control checks and/or binnedby, for example, output power and/or emission wavelength. The device maybe incorporated into a larger system that advantageously uses theemitted UV light by the device fabricator or by a third-party customerto whom the device is transferred (e.g., sold and shipped). For example,the larger system may include or consist essentially of a disinfection,purification, and/or biocidal system for liquids and/or gases, a medicaldevice, an imaging system (e.g., an anti-counterfeiting system forexamination of watermarks on currency), a UV curing system, a printingsystems, an optical sensor, etc.

In various embodiments of the invention, after the burn-in periodexposing the organic encapsulant to UV light, the output power of thedevices is measured in order to enable rejection of devices exhibitingless output power than a criterion (i.e., than a predetermined minimumdesired output power). This measurement step is typically performed as atest in the manufacturing process before the devices are shipped tocustomers. Approximately 20% to approximately 40% of the burned-indevices may show lower output power than the minimum output powercriterion due to, for example, variability of the conversion of organicencapsulant into non-stoichiometric silica during the burn-in period.That is, during or after the burn-in procedure detailed herein, somepercentage of the devices may exhibit power degradation, although themajority of the devices maintain output powers nearly equal to theoutput powers before burn-in. Therefore, the test step following theburn-in procedure may advantageously be utilized to eliminate (e.g.,remove from a shipment to a customer) low-output-power devices that donot meet product specifications.

Furthermore, various embodiments of the invention may utilize, duringthe burn-in conversion procedure, one or more operating conditionsdifferent from those to be utilized by the light-emitting device duringnormal operation (i.e., operation by a customer and/or operation withina larger device advantageously utilizing the UV light emitted by thedevice). For example, a higher current or higher temperature conditionthan those recommended as maximum operation conditions may be applied inthe burn-in step in order to accelerate the conversion intonon-stoichiometric silica material. In one exemplary embodiment, whilethe maximum recommended operating current of a UV light-emitting deviceis 300 mA, a larger current (e.g., 400 mA) may be applied for all orpart of the burn-in procedure (e.g., for 100 hours) to facilitate theconversion of the organic encapsulant material. In another exemplaryembodiment, while the recommended maximum case temperature of a UVlight-emitting device is 55° C., a case temperature higher than therecommended maximum (e.g., 85° C.) may be applied during all or part ofthe burn-in procedure to facilitate the conversion of the organicencapsulant material.

Another operating condition that may be varied during the burn-inprocedure from that utilized during normal operation is the oxygenconcentration in the atmosphere surrounding the light-emitting device.For example, the burn-in procedure may be performed under an atmospherehaving a higher oxygen concentration atmosphere than that utilizedduring normal operation (e.g., atmospheric air). As detailed herein, invarious embodiments of the present invention the organic encapsulant isconverted into non-stoichiometric silica material via a photochemicaloxidation reaction; thus, introducing excessive oxygen as an oxidantpromotes the conversion reaction. In various embodiments, the atmospherein which the burn-in procedure is performed may include more than 30%oxygen up to 100% of oxygen.

In various embodiments of the invention, silicone resin is used as theUV-transparent encapsulant. In such cases, the photochemical reactionthat enables conversion of silicone into non-stoichiometric silicamaterial may form formaldehyde as a byproduct. Therefore, variousembodiments of the invention balance the generation of the byproductformaldehyde and the outward diffusion of the formaldehyde, becauseaccumulation of formaldehyde may result in formation of bubbles (e.g.,having a size of a few nanometers to tens of microns) that may block ordeflect UV light emitted by the semiconductor die, decreasing deviceefficiency. If diffusion of formaldehyde being generated during theburn-in procedure is much slower than formation of the formaldehyde, theconversion process may be more unstable due to accumulation offormaldehyde in the non-stoichiometric silica material. Thus, in suchcases, all or part of the burn-in procedure may be performed utilizingoperating currents and/or temperatures lower than those recommended fornominal device operation (i.e., by a customer). In an exemplaryembodiment, for devices with recommended operating current of 300 mA, alower current of, e.g., 20 mA to 150 mA may be utilized for all or partof the burn-in procedure to reduce the formation rate of formaldehydeand consequently avoid accumulation of formaldehyde that mightdetrimentally impact light output power.

In other embodiments, the diffusion of formaldehyde is enhanced in orderto avoid accumulation of formaldehyde generated in the burn-inprocedure. As described above, a higher case temperature (i.e., thetemperature applied to the semiconductor die and/or part or all of itspackaging, such as a submount) may increase the rate of diffusion of theformaldehyde out of the encapsulant undergoing conversion. In additionor alternatively, all or part of the burn-in procedure may be performedin a vacuum atmosphere in order to promote diffusion of the formaldehydebyproduct out of the unconverted and/or converted encapsulant.

In various other embodiments, the rate of the photochemical conversionreaction is reduced to increase the diffusion of formaldehyde relativeto its formation by limiting oxygen concentration in the encapsulant.For oxidation reactions, oxygen may be utilized as an oxidant. Sourcesof oxygen include oxygen molecules dissolved in the encapsulant materialand/or oxygen molecules being diffused inward from the atmosphere duringburn-in. In various embodiments, limiting oxygen concentration in theencapsulant is effective in reducing the rate of photochemical reaction.In such embodiments, oxygen concentration in the encapsulant is limitedto between 0.1 ppm to 1 atomic %. To attain such low oxygenconcentrations, preparation of the encapsulant material, including anykneading steps, may be performed under a low-oxygen atmosphere (e.g., anatmosphere containing between 0% and 10% oxygen), e.g., under asubstantially pure nitrogen (or inert gas) atmosphere.

In various embodiments of the present invention, particularly when theoutput power of the light-emitting device before burn-in is greater than15 mW, the device may exhibit an output power recovery phenomenon. Insuch a recovery phenomenon, the output power may initially decreaseduring the first stages of the burn-in but then increase during laterstages of the burn-in. Although the inventors do not wish to be boundby, and embodiments of the invention are not limited by, the mechanismfor the recovery, the following describes one possible mechanism. In theinitial stages of the burn-in, formaldehyde accumulation may cause adecrease in output power due to bubble formation. At a later stage ofburn-in, as the photochemical reaction dwindles as the conversion of theencapsulant is completed, outward diffusion of formaldehyde becomesrelatively faster than formation of the formaldehyde, resulting inelimination of bubbles including or consisting essentially offormaldehyde gas, thereby enabling the output power recovery. Therefore,embodiments of the invention monitor the output power of the deviceduring the burn-in procedure and utilize burn-in times longer than thatrequired for the output power of the device to recover to a level closeto (e.g., approximately 80% to approximately 100%) the initial outputpower level when the burn-in commences. The burn-in period that enablesrecovery may depend on the output power of the device undergoingburn-in. For example, a device having an output power of 20 mW beforeburn-in may utilize a burn-in of at least 200 hours, while a devicehaving an output power of 15 mW may utilize a burn-in of at least 300hours.

Example 1

Silicone resin was utilized as an organic encapsulant and dispensed overa UV LED die in a lead-frame package. A rigid hemispherical lenscomposed of fused silica was attached to the die via application offorce sufficient to minimize the thickness of silicone resin between thelens and the die. The device with the silicone resin and the lens wasplace in a vacuum oven under 10 Torr of vacuum at room temperature for10 minutes to remove any air trapped in the silicone resin. The devicewas baked in an oven at approximately 150° C. for approximately 1 hourin order to cure the silicone resin. In this example, the resultingthickness of the silicone resin was approximately 8 μm. Epoxy resin wasdispensed as an attachment material, filling the lead-frame cavity,covering the wire bonds to the LED die, and slightly overlapping, andextending over, the bottom surface of the rigid lens. The device wasthen baked in an oven at 160° C. for 1 hour to cure the epoxy resin. Thetop surface of the cured epoxy resin extended above the bottom surfaceof the rigid lens by 0.2 mm. The silicone resin was exposed to UV lighthaving a wavelength of 265 nm emitted by the LED die for 200 hours toconvert the silicone resin into non-stoichiometric silica material. Thecarbon content of the resulting non-stoichiometric silica material wasabout 20 atomic %.

Example 2

Silicone resin was utilized as an organic encapsulant and dispensed overa UV LED die in a lead-frame package. A rigid hemispherical lenscomposed of fused silica was attached to the die via application offorce sufficient to minimize the thickness of silicone resin between thelens and the die. The device with the silicone resin and the lens wasplace in a vacuum oven under 10 Torr of vacuum at room temperature for10 minutes to remove any air trapped in the silicone resin. The devicewas baked in an oven at approximately 150° C. for approximately 1 hourin order to cure the silicone resin. In this example, the resultingthickness of the silicone resin was approximately 8 μm. The siliconeresin was exposed to UV light having a wavelength of 265 nm emitted bythe LED die for 200 hours to convert the silicone resin intonon-stoichiometric silica material. The carbon content of the resultingnon-stoichiometric silica material was about 20 atomic %.

The terms and expressions employed herein are used as terms ofdescription and not of limitation, and there is no intention, in the useof such terms and expressions, of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theinvention claimed.

What is claimed is: 1.-68. (canceled)
 69. An illumination devicecomprising: an ultraviolet (UV) light-emitting semiconductor die; and alayer of non-stoichiometric silica material disposed over and/or aroundthe semiconductor die, wherein the non-stoichiometric silica materialcomprises silicon, oxygen, and carbon, a carbon content of thenon-stoichiometric silica material being greater than 1 ppm and lessthan 40 atomic percent.
 70. The illumination device of claim 69, whereinthe carbon content of the non-stoichiometric silica material is greaterthan 1 atomic percent.
 71. The illumination device of claim 69, whereinthe carbon content of the non-stoichiometric silica material is lessthan 20 atomic percent.
 72. The illumination device of claim 69, whereinthe layer of non-stoichiometric silica material is disposed over a topsurface of the semiconductor die, and further comprising a barriermaterial disposed proximate a sidewall of the semiconductor die, thebarrier material being opaque to UV light.
 73. The illumination deviceof claim 72, wherein the barrier material comprises aluminum,polytetrafluoroethylene, and/or an opaque resin.
 74. The illuminationdevice of claim 69, wherein the non-stoichiometric silica materialconsists of silicon, oxygen, and carbon.
 75. The illumination device ofclaim 69, wherein the non-stoichiometric silica material is shaped as alens.
 76. The illumination device of claim 69, wherein thenon-stoichiometric silica material is shaped as a flat plate.
 77. Theillumination device of claim 69, wherein the non-stoichiometric silicamaterial comprises therewithin a plurality of scattering centers eachhaving a refractive index different from a refractive index of thenon-stoichiometric silica material.
 78. The illumination device of claim69, further comprising an attachment material disposed around at least aportion of the semiconductor die and around at least a portion of thenon-stoichiometric silica material.
 79. The illumination device of claim78, wherein the attachment material comprises a resin.
 80. Theillumination device of claim 78, wherein the attachment material isopaque to UV light.
 81. The illumination device of claim 78, wherein theattachment material comprises at least one of a mechanical fastener or aclamp.
 82. An illumination device comprising: an ultraviolet (UV)light-emitting semiconductor die; and a layer of encapsulant disposedover and/or around the semiconductor die, wherein (i) a first portion ofthe layer of encapsulant comprises a non-stoichiometric silica material,(ii) a second portion of the layer of encapsulant comprises silicone,and (iii) the non-stoichiometric silica material comprises silicon,oxygen, and carbon, a carbon content of the non-stoichiometric silicamaterial being greater than 1 ppm and less than 40 atomic percent. 83.The illumination device of claim 82, wherein the carbon content of thenon-stoichiometric silica material is greater than 1 atomic percent. 84.The illumination device of claim 82, wherein the carbon content of thenon-stoichiometric silica material is less than 20 atomic percent. 85.The illumination device of claim 82, wherein the first portion of thelayer of encapsulant is disposed over a top surface of the semiconductordie and the second portion of the layer of encapsulant is disposedproximate a sidewall of the semiconductor die.
 86. The illuminationdevice of claim 85, further comprising a barrier material between thesidewall of the semiconductor die and the second portion of the layer ofencapsulant, the barrier material being opaque to UV light.
 87. Theillumination device of claim 86, wherein the barrier material comprisesaluminum, polytetrafluoroethylene, and/or an opaque resin.
 88. Theillumination device of claim 82, wherein the non-stoichiometric silicamaterial consists of silicon, oxygen, and carbon.